CN117042334A - Silver plating lamination method for printed circuit board substrate - Google Patents
Silver plating lamination method for printed circuit board substrate Download PDFInfo
- Publication number
- CN117042334A CN117042334A CN202311291637.6A CN202311291637A CN117042334A CN 117042334 A CN117042334 A CN 117042334A CN 202311291637 A CN202311291637 A CN 202311291637A CN 117042334 A CN117042334 A CN 117042334A
- Authority
- CN
- China
- Prior art keywords
- silver
- coupling agent
- copper
- silver plating
- silane coupling
- Prior art date
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Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000007747 plating Methods 0.000 title claims abstract description 104
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 104
- 239000004332 silver Substances 0.000 title claims abstract description 104
- 239000000758 substrate Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000003475 lamination Methods 0.000 title claims abstract description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 69
- 238000001035 drying Methods 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 43
- -1 methacryloxy Chemical group 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 24
- 239000002985 plastic film Substances 0.000 claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000010030 laminating Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 93
- 239000000243 solution Substances 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 39
- 229910021641 deionized water Inorganic materials 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 25
- 238000003825 pressing Methods 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 239000004743 Polypropylene Substances 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000007822 coupling agent Substances 0.000 claims description 22
- 229920001155 polypropylene Polymers 0.000 claims description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012670 alkaline solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 238000009833 condensation Methods 0.000 abstract description 7
- 230000005494 condensation Effects 0.000 abstract description 7
- 230000018044 dehydration Effects 0.000 abstract description 5
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 8
- 239000001433 sodium tartrate Substances 0.000 description 8
- 229960002167 sodium tartrate Drugs 0.000 description 8
- 235000011004 sodium tartrates Nutrition 0.000 description 8
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
Abstract
The application discloses a silver plating lamination method for a printed circuit board substrate, which belongs to the field of surface treatment, and comprises the steps of immersing a copper-clad plate in chemical silver plating liquid containing a sulfhydryl silane coupling agent, reacting to obtain a silver-plated plate with the surface modified with the silane coupling agent, immersing the silver-plated plate in a second solution containing a methacryloxy silane coupling agent, drying to obtain a modified substrate self-assembled with a methacryloxy molecular chain, and finally laminating the modified substrate with a plastic sheet immersed with a resin adhesive. According to the method, a sulfhydryl silane coupling agent is added into chemical silver plating solution, sulfhydryl groups are easy to combine with silver ions, after silver plating is carried out on a copper-clad plate, a silane coupling agent chain segment is grafted/modified on the surface of the obtained silver-clad plate, after soaking and drying in a second solution, the methacryloxy silane coupling agent and the sulfhydryl silane coupling agent undergo dehydration condensation, and a methacryloxy group which is easy to combine with resin strongly is self-assembled on the surface of the silver-clad plate, so that a silver-plated layer and a plastic sheet are well combined after lamination.
Description
Technical Field
The application relates to a silver plating lamination method for a printed circuit board substrate, and belongs to the field of surface treatment.
Background
The base material of the Printed Circuit Board (PCB) is a copper clad laminate, and a required copper foil circuit is manufactured through etching. Because of the oxygen and water vapor in the air, the thin copper layer is exposed to the air for a long time and is easy to be subjected to damp and oxidation, so that the copper layer becomes a poor conductor of electricity, and the electrical performance of the PCB is greatly damaged. The lamination process can be used for manufacturing a multi-layer circuit board, and can also be used for enhancing the board mechanical strength of a PCB, covering and protecting a copper layer.
With the rapid development of circuit integration, the requirements for the conductive characteristics of the circuit are increasingly high, and silver with good conductivity is widely used. Plating a silver layer on the surface of the copper line is beneficial to improving the conductive property of the line, and meanwhile, the copper line can be prevented from being damaged in the subsequent welding process, so that the transmission loss is reduced. However, when the silver-plated plastic sheet is pressed with a plastic sheet such as polypropylene, the binding force between the silver-plated layer and the resin layer is poor, which is not beneficial to the reliable production and application of the PCB.
Disclosure of Invention
In order to overcome the defects of the prior art, the application provides a silver plating lamination method for a printed circuit board substrate, which solves the problem of poor bonding force between a silver plating layer and a resin layer.
The technical scheme adopted for solving the technical problems is as follows:
the application provides a silver plating lamination method for a printed circuit board substrate, which comprises the following steps:
immersing the copper-clad plate into chemical silver plating liquid containing a sulfhydryl silane coupling agent, and cleaning and drying after the reaction to obtain a silver-plated plate with the surface modified with the silane coupling agent;
immersing the silver plate into a second solution containing a methacryloxy silane coupling agent, and drying after the reaction to obtain a modified substrate self-assembled with a methacryloxy molecular chain;
and pressing the modified substrate and the plastic sheet immersed with the resin adhesive.
According to the silver plating press-fit method for the printed circuit board substrate, the sulfhydryl silane coupling agent is added into the chemical silver plating solution, sulfhydryl groups are easy to combine with silver ions, after silver plating is carried out on the copper-clad plate, the surface of the obtained silver-plated plate is grafted with the silane coupling agent chain segments, after soaking and drying in the second solution, the methacryloxy silane coupling agent and the sulfhydryl silane coupling agent undergo dehydration condensation, and the methacryloxy groups which are easy to combine with resin strongly are assembled on the surface of the silver-plated plate, so that the silver-plated layer after press-fit can be well combined with the plastic sheet.
Further, the copper-clad plate is subjected to pretreatment, and the pretreatment step comprises the following steps:
degreasing the copper-clad plate by using an alkaline solution, cleaning the copper-clad plate by using deionized water and ethanol in sequence, and drying; and then microetching the copper-clad plate by using an acid solution, cleaning the copper-clad plate by using deionized water and ethanol in sequence, and drying the copper-clad plate.
The copper surface impurity can be removed easily by degreasing and microetching, and the copper with reactivity can be fully exposed.
Further, the step of degreasing the copper-clad plate with an alkaline solution includes:
and (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min.
Further, the step of microetching the copper-clad plate with an acidic solution includes:
and microetching the copper-clad plate for 1min by using 125g/L sodium persulfate solution.
Further, the chemical silver plating solution also comprises a complexing agent, a reducing agent and 1-10 wt% of silver nitrate.
The concentration of silver nitrate in the conventional silver plating solution is about 0.5 wt%. According to the silver plating method, silver nitrate is required to be added into a solution containing the mercaptosilane coupling agent, the mercaptosilane coupling agent is a component which is not contained in conventional silver plating solution, the silver plating effect is affected to a certain extent, and the concentration of the silver nitrate is set to be 1-10wt% through experiments, so that the silver plating layer which can be strongly combined with the mercaptosilane coupling agent is formed. The concentrations of complexing agent and reducing agent can be scaled in equal proportion (the ratio of the concentration of silver nitrate in the application to the concentration of silver nitrate in conventional silver plating solutions). Wherein the complexing agent can be ethylenediamine or disodium ethylenediamine tetraacetate; the reducing agent may be selected from formaldehyde, sodium tartrate, glyoxal, triethanolamine or glucose.
Further, the preparation method of the electroless silver plating solution comprises the following steps:
mixing absolute ethyl alcohol and deionized water to obtain a first solvent, and dissolving a mercaptosilane coupling agent in the first solvent according to the concentration of 1-15wt% to obtain a first solution, wherein the ratio of the mercaptosilane coupling agent to the deionized water is 1:1-5;
adding the silver nitrate while stirring the first solution;
and adding the complexing agent and the reducing agent to obtain the chemical silver plating solution.
Based on the silver nitrate with the concentration of 1-10wt% in the chemical silver plating solution, the mercapto silane coupling agent with the concentration is beneficial to enhancing the combination effect of the mercapto silane coupling agent and the silver plating layer.
Further, the steps of immersing the copper-clad plate into the chemical silver plating solution containing the sulfhydryl silane coupling agent, and cleaning and drying after the reaction comprise the following steps:
immersing the copper-clad plate into chemical silver plating liquid containing a sulfhydryl silane coupling agent, reacting for 0.5-3 h at 20-60 ℃, washing with absolute ethyl alcohol, and drying to ensure that silver ions and the sulfhydryl silane coupling agent fully react to form S-Ag bonding. And in the step, baking is not adopted, so that self-phase coupling of the sulfhydryl silane coupling agent is avoided.
Further, the preparing step of the second solution includes:
mixing absolute ethyl alcohol and deionized water to obtain a second solvent, dissolving a methacryloxy silane coupling agent in the second solvent according to the concentration of 1-15 wt%, and regulating the pH to 3-5 by acetic acid to obtain a second solution, wherein the ratio of the methacryloxy silane coupling agent to the deionized water is 1:1-5.
The silver plating layer prepared from the chemical silver plating solution containing the mercapto silane coupling agent adopts the methacryloxy silane coupling agent with the concentration, is favorable for dehydration condensation of the mercapto silane coupling agent and the methacryloxy silane coupling agent, and is favorable for improving the mechanical strength and weather resistance of the PCB.
Further, the step of immersing the silver plate in a second solution containing a methacryloxy silane coupling agent, and drying after the reaction comprises the following steps:
immersing the silver plate into a second solution containing a methacryloxy silane coupling agent, reacting for 5min-60min at 20-60 ℃, and then baking for 0.5h-3h in an environment of 50-100 ℃.
Further, the step of pressing the modified substrate with the plastic sheet impregnated with the resin adhesive includes:
and pressing the modified substrate with a polypropylene plastic sheet immersed with a resin adhesive or a polyimide plastic sheet immersed with the resin adhesive, wherein the pressure is 2MPa-20MPa, the temperature is 150-240 ℃, and the pressing time is 0.5-5 h.
The beneficial effects of the application are as follows: according to the silver plating lamination method for the printed circuit board substrate, the chemical silver plating solution containing the sulfhydryl silane coupling agent is used for plating silver on the copper-clad plate, sulfhydryl groups are easy to combine with silver ions to form S-Ag bonding, the sulfhydryl silane coupling agent is directly added into the chemical silver plating solution, the grafting modification effect on the silver plating layer is better, the surface of the silver-plated plate obtained after silver plating is modified with silane coupling agent chain segments (the tail ends of the chain segments are silica groups), then the methacryloxy silane coupling agent is used for dehydrating condensation self-assembly of the silver plating layer after the butt joint modification, the tail ends of the methacryloxy groups are easy to combine with resin strongly, and further, the chemical bonding between the silver plating layer and the resin can be established through the two silane coupling agents, so that the chemical bonding effect between the silver plating layer and the resin is enhanced, and the lamination effect between the copper-plated silver-plated substrate and the plastic plate is ensured, and the printed circuit board with good and stable performance is obtained.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. The objectives and other advantages of the application may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
Fig. 1 is a flowchart of steps of a method for silver plating and laminating a printed circuit board substrate according to an embodiment of the present application.
Detailed Description
The following detailed description of embodiments of the application, examples of which are illustrated in the accompanying drawings and, with reference to the drawings, are exemplary only and are not to be construed as limiting the application.
Silver plating on the copper lines can enhance the conductive properties of the circuit board. The plastic sheet is used for pressing the PCB board to manufacture a multi-layer circuit board, and the mechanical strength of the PCB board can be enhanced. However, these two improvements are difficult to apply together because the silver coating is difficult to bond with the resin adhesive commonly used in lamination processes.
In view of the above problems, referring to fig. 1, an embodiment of the present application provides a silver plating lamination method for a printed circuit board substrate, including the following steps:
s1: immersing the copper-clad plate into chemical silver plating liquid containing a sulfhydryl silane coupling agent, and drying after reaction to obtain the silver-clad plate with the surface modified with the silane coupling agent. The method comprises the steps of plating silver on a copper-clad plate by using chemical silver plating liquid containing a sulfhydryl silane coupling agent, wherein sulfhydryl can form S-Ag bond with silver ions, and the sulfhydryl silane coupling agent is grafted on the surface of the silver layer. Experiments prove that the effect of grafting modification on the silver plating layer is better by directly adding the sulfhydryl silane coupling agent into the chemical silver plating solution.
S2: immersing the silver plate into a second solution containing the methacryloxy silane coupling agent, reacting and drying to obtain the modified substrate self-assembled with the methacryloxy molecular chains. In this step, a methacryloxy group capable of bonding to a resin is self-assembled by dehydrating condensation of a methacryloxy silane coupling agent and a mercaptosilane coupling agent.
S3: and pressing the modified substrate and the plastic sheet immersed with the resin adhesive. The methacryloxy groups can be tightly combined with the plastic sheet, so that the silver plating layer and the plastic sheet can be well combined, and the mechanical strength and weather resistance of the material are improved.
Preferably, the copper-clad plate is pretreated, and the pretreatment step comprises the following steps:
degreasing the copper-clad plate by using an alkaline solution, cleaning the copper-clad plate by using deionized water and ethanol in sequence, and drying; and then microetching the copper-clad plate by using an acid solution, cleaning the copper-clad plate by using deionized water and ethanol in sequence, and drying the copper-clad plate. The alkaline solution may be sodium hydroxide and/or sodium carbonate solution; the acidic solution may be sulfuric acid, sulfate, persulfate, etc.
In a preferred embodiment, the copper-clad plate is placed in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min. Then microetching the copper-clad plate for 1min by using 125g/L sodium persulfate solution.
The preparation method of the electroless silver plating solution comprises the following steps: mixing absolute ethyl alcohol and deionized water to obtain a first solvent, and dissolving a mercaptosilane coupling agent in the first solvent according to the concentration of 1-15wt% to obtain a first solution, wherein the ratio of the mercaptosilane coupling agent to the deionized water is 1:1-5; adding silver nitrate while stirring the first solution; then adding complexing agent and reducing agent to obtain chemical silver plating solution, wherein silver nitrate accounts for 1-10wt% of the chemical silver plating solution.
The preparation step of the second solution comprises the following steps: mixing absolute ethyl alcohol and deionized water to obtain a second solvent, dissolving a methacryloxy silane coupling agent in the second solvent according to the concentration of 1-15 wt%, and regulating the pH to 3-5 by acetic acid to obtain a second solution, wherein the ratio of the methacryloxy silane coupling agent to the deionized water is 1:1-5.
It should be noted that the chemical silver plating solution is prepared based on the solution (first solution) of the mercapto silane coupling agent, so that the grafting modification effect on the silver plating layer is better. More preferably, the concentration of silver nitrate in the electroless silver plating solution is 1wt% to 10wt%; the concentration of the methacryloxy silane coupling agent in the second solution is 1-15 wt%, which is equivalent to the dosage of the mercapto silane coupling agent in the chemical silver plating solution, thus being beneficial to silver being densely plated on a copper wire, and the dehydration condensation self-assembled silane coupling agent is tightly combined with a silver plating layer through mercapto.
The step S1 specifically comprises the following steps: immersing the copper-clad plate into chemical silver plating liquid containing a sulfhydryl silane coupling agent, reacting for 0.5-3 h at 20-60 ℃, washing with absolute ethyl alcohol, and drying to obtain the silver-clad plate with the surface modified with the silane coupling agent. The method is favorable for quick drying by washing with absolute ethyl alcohol, the ethyl alcohol is a part of the solvent in the chemical silver plating solution and the second solution, no new impurity is introduced, drying is not adopted in the step, self-phase coupling of the mercapto silane coupling agent is avoided, and the silver plate is ensured to have enough grafted chain segments with silicon oxygen groups at the tail ends.
The step S2 specifically comprises the following steps: immersing the silver plate into a second solution containing a methacryloxy silane coupling agent, reacting for 5min-60min at 20-60 ℃, and then baking for 0.5h-3h in an environment of 50-100 ℃.
The step S3 specifically comprises the following steps: pressing the modified substrate with a polypropylene plastic sheet immersed with a resin adhesive or a polyimide plastic sheet immersed with the resin adhesive, wherein the pressure is 2MPa-20MPa, the temperature is 150-240 ℃, and the pressing time is 0.5-5 h.
Example 1
And (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min, and cleaning with deionized water and ethanol and drying. Then microetching in 125g/L sodium persulfate solution for 1min, washing with deionized water and ethanol, and drying for later use. Adding 1.5g of (3-mercaptopropyl) triethoxysilane coupling agent into 100ml of a first solvent prepared from absolute ethyl alcohol and deionized water, magnetically stirring, adding 1.5g of silver nitrate in the stirring process, uniformly mixing, then adding 2g of ethylenediamine, 1.5g of disodium ethylenediamine tetraacetate and 1.5g of sodium tartrate, magnetically stirring to completely dissolve, and preparing the chemical silver plating solution containing the mercaptosilane coupling agent. Immersing the microetched copper-clad plate into chemical silver plating solution, plating for 60min at the water bath temperature of 45 ℃, and cleaning and drying by absolute ethyl alcohol after the completion of the plating to obtain the silver-clad plate. Preparing a 5wt% methacryloxy trimethoxy silane ethanol mixed solution, regulating the pH value to 4 by acetic acid, immersing the silver plate into the mixed solution for 30min, taking out the silver plate, and putting the silver plate into an oven for curing at 80 ℃ for 60min to obtain the modified substrate. And (3) pressing the modified substrate and the polypropylene sheet immersed with the resin adhesive by using a vacuum hot-press forming machine, wherein the temperature is 220 ℃, the pressure is 3MPa, and the pressing time is 60 minutes. And after lamination, a cross-hatch experiment is carried out on the polypropylene sheet, no small lattice is fallen off, and good combination of the copper-clad silver-plated plate and the polypropylene sheet is realized. And placing the laminated plate in a constant temperature and humidity test box with 85 ℃ and 85% of humidity R.H. for 100 hours, wherein the plate has no bubbling layering phenomenon.
Example 2
And (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min, and cleaning with deionized water and ethanol and drying. Then microetching in 125g/L sodium persulfate solution for 1min, washing with deionized water and ethanol, and drying for later use. Adding 3g of (3-mercaptopropyl) triethoxysilane coupling agent into 100ml of a first solvent prepared from absolute ethyl alcohol and deionized water, magnetically stirring, adding 1.5g of silver nitrate in the stirring process, uniformly mixing, adding 2g of ethylenediamine, 1.5g of disodium edetate and 1.5g of sodium tartrate, magnetically stirring to completely dissolve, and preparing the chemical silver plating solution containing the mercaptosilane coupling agent. Immersing the microetched copper-clad plate into chemical silver plating solution, plating for 60min at the water bath temperature of 45 ℃, and cleaning and drying by absolute ethyl alcohol after the completion of the plating to obtain the silver-clad plate. Preparing a 5wt% methacryloxy trimethoxy silane ethanol mixed solution, regulating the pH value to 4 by acetic acid, immersing the silver plate into the mixed solution for 30min, taking out the silver plate, and putting the silver plate into an oven for curing at 80 ℃ for 60min to obtain the modified substrate. And (3) pressing the modified substrate and the polypropylene sheet immersed with the resin adhesive by using a vacuum hot-press forming machine, wherein the temperature is 220 ℃, the pressure is 3MPa, and the pressing time is 60 minutes. And after lamination, a cross-hatch experiment is carried out on the polypropylene sheet, no small lattice is fallen off, and good combination of the copper-clad silver-plated plate and the polypropylene sheet is realized.
Example 3
And (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min, and cleaning with deionized water and ethanol and drying. Then microetching in 125g/L sodium persulfate solution for 1min, washing with deionized water and ethanol, and drying for later use. Adding 3g of (3-mercaptopropyl) triethoxysilane coupling agent into 100ml of a first solvent prepared from absolute ethyl alcohol and deionized water, magnetically stirring, adding 1.5g of silver nitrate in the stirring process, uniformly mixing, adding 2g of ethylenediamine, 1.5g of disodium edetate and 1.5g of sodium tartrate, magnetically stirring to completely dissolve, and preparing the chemical silver plating solution containing the mercaptosilane coupling agent. Immersing the microetched copper-clad plate into chemical silver plating solution, plating for 60min at the water bath temperature of 45 ℃, and cleaning and drying by absolute ethyl alcohol after the completion of the plating to obtain the silver-clad plate. Preparing 10wt% of methacryloxy trimethoxy silane ethanol mixed solution, regulating the pH value to 4 by acetic acid, immersing the silver plate into the mixed solution for 30min, taking out the silver plate, and putting the silver plate into an oven for curing at 80 ℃ for 60min to obtain the modified substrate. And (3) pressing the modified substrate and the polypropylene sheet immersed with the resin adhesive by using a vacuum hot-press forming machine, wherein the temperature is 220 ℃, the pressure is 3MPa, and the pressing time is 60 minutes. And after lamination, a cross-hatch experiment is carried out on the polypropylene sheet, no small lattice is fallen off, and good combination of the copper-clad silver-plated plate and the polypropylene sheet is realized.
Comparative example 1
And (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min, and cleaning with deionized water and ethanol and drying. Then microetching in 125g/L sodium persulfate solution for 1min, washing with deionized water and ethanol, and drying for later use. 1.5g of silver nitrate, 2g of ethylenediamine, 1.5g of disodium ethylenediamine tetraacetate and 1.5g of sodium tartrate were added to 100ml of deionized water, and the mixture was magnetically stirred to be completely dissolved, and then the pH=12 of the solvent was adjusted with 24g/L of sodium hydroxide solution to prepare a electroless silver plating solution. Immersing the microetched copper-clad plate into chemical silver plating solution, plating for 60min at the water bath temperature of 45 ℃, and cleaning and drying by absolute ethyl alcohol after the completion of the plating to obtain the silver-clad plate. And (3) pressing the silver plate and the polypropylene sheet immersed with the resin adhesive by using a vacuum hot-press forming machine, wherein the temperature is 220 ℃, the pressure is 3MPa, and the pressing time is 60 minutes. The copper-clad silver-plated plate and the polypropylene sheet cannot be bonded together.
Comparative example 2
And (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min, and cleaning with deionized water and ethanol and drying. Then microetching in 125g/L sodium persulfate solution for 1min, washing with deionized water and ethanol, and drying for later use. 1.5g of silver nitrate, 2g of ethylenediamine, 1.5g of disodium ethylenediamine tetraacetate and 1.5g of sodium tartrate are added into 100ml of deionized water, and the mixture is magnetically stirred to be completely dissolved, so that chemical silver plating liquid is prepared. Immersing the microetched copper-clad plate into chemical silver plating solution, plating for 60min at the water bath temperature of 45 ℃, and cleaning and drying by absolute ethyl alcohol after the completion of the plating to obtain the silver-clad plate. Immersing the silver plate into 5wt% (3-mercaptopropyl) triethoxysilane coupling agent ethanol solution for 30min, taking out, and cleaning and drying by using absolute ethanol. Then preparing a 5wt% methacryloxy trimethoxy silane ethanol mixed solution, regulating the pH value to 4 by acetic acid, immersing a silver plate immersed in the ethanol solution of the (3-mercaptopropyl) triethoxy silane coupling agent for 30min, taking out, putting into an oven, and curing at 80 ℃ for 60min to obtain the modified substrate. And (3) pressing the modified substrate and the polypropylene sheet immersed with the resin adhesive by using a vacuum hot-press forming machine, wherein the temperature is 220 ℃, the pressure is 3MPa, and the pressing time is 60 minutes. After lamination, a cross-hatch test is carried out on the polypropylene sheet, and 5% of the cells fall off.
Comparative example 3
And (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min, and cleaning with deionized water and ethanol and drying. Then microetching in 125g/L sodium persulfate solution for 1min, washing with deionized water and ethanol, and drying for later use. Adding 3g of vinyl triethoxysilane coupling agent into 100ml of a first solvent prepared from absolute ethyl alcohol and deionized water, magnetically stirring, adding 1.5g of silver nitrate in the stirring process, uniformly mixing, adding 2g of ethylenediamine, 1.5g of disodium ethylenediamine tetraacetate and 1.5g of sodium tartrate, magnetically stirring to completely dissolve, and preparing the chemical silver plating solution containing the vinyl triethoxysilane coupling agent. Immersing the microetched copper-clad plate into chemical silver plating solution, plating for 60min at the water bath temperature of 45 ℃, and cleaning and drying by absolute ethyl alcohol after the completion of the plating to obtain the silver-clad plate. Preparing a 5wt% methacryloxy trimethoxy silane ethanol mixed solution, regulating the pH value to 4 by acetic acid, immersing the silver plate into the mixed solution for 30min, taking out the silver plate, and putting the silver plate into an oven for curing at 80 ℃ for 60min to obtain the modified substrate. And (3) pressing the modified substrate and the polypropylene sheet immersed with the resin adhesive by using a vacuum hot-press forming machine, wherein the temperature is 220 ℃, the pressure is 3MPa, and the pressing time is 60 minutes. And (3) after lamination, carrying out a cross-hatch experiment on the polypropylene sheet, wherein more than 90% of the lattices fall off.
Comparative example 4
And (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min, and cleaning with deionized water and ethanol and drying. Then microetching in 125g/L sodium persulfate solution for 1min, washing with deionized water and ethanol, and drying for later use. Adding 3g of (3-mercaptopropyl) triethoxysilane coupling agent into 100ml of a first solvent prepared from absolute ethyl alcohol and deionized water, magnetically stirring, adding 1.5g of silver nitrate in the stirring process, uniformly mixing, adding 2g of ethylenediamine, 1.5g of disodium ethylenediamine tetraacetate and 1.5g of sodium tartrate, magnetically stirring to completely dissolve, and preparing the chemical silver plating solution containing the (3-mercaptopropyl) triethoxysilane coupling agent. Immersing the microetched copper-clad plate into chemical silver plating solution, plating for 60min at the water bath temperature of 45 ℃, and cleaning and drying by absolute ethyl alcohol after the completion of the plating to obtain the silver-clad plate. Preparing a 5wt% gamma-aminopropyl triethoxysilane ethanol mixed solution, immersing the silver plate in the mixed solution for 30min, taking out the silver plate, putting the silver plate into an oven, and curing the silver plate at 80 ℃ for 60min to obtain the modified substrate. And (3) pressing the modified substrate and the polypropylene sheet immersed with the resin adhesive by using a vacuum hot-press forming machine, wherein the temperature is 220 ℃, the pressure is 3MPa, and the pressing time is 60 minutes, so that the good combination of the copper-clad silver-plated plate and the polypropylene sheet is realized. And placing the laminated plate in a constant temperature and humidity test box with 85 ℃ and 85% of humidity R.H. for 100 hours, wherein the foaming delamination phenomenon occurs between the polypropylene sheet and the silver coating.
Comparing examples 1 to 3 with comparative examples 1 to 4, it was found that example 1, example 2 and example 3 each achieved good bonding of the silver plating layer and the plastic sheet. Although the comparative example 2 also uses the mercapto silane coupling agent and the methacryloxy silane coupling agent, the silver nitrate and the mercapto silane coupling agent are not mixed, and the silver and the mercapto silane coupling agent are combined to the surface of the copper-clad plate in sequence, so that the combination effect is poor, and the silver and the mercapto silane coupling agent can fall off after the dicing experiment is performed. Comparative example 3 and comparative example 4 do not select the combination of mercaptosilane coupling agent and methacryloxy silane coupling agent, and comparative example 3 has poor bonding effect, and comparative example 4 has poor weather resistance of the finished product, although good bonding of silver plating layer and plastic sheet can be achieved, compared to example 1.
According to the embodiment of the application, the surface of the chemical silver coating is modified step by utilizing the mercapto silane coupling agent and the methacryloxy silane coupling agent, and a molecular chain capable of generating chemical bonding with a plastic sheet is formed on the surface of the silver coating through chemical grafting and dehydration condensation self-assembly, so that good bonding between the mercapto silane coupling agent and the plastic sheet is realized, the performance of a PCB is improved, the mechanical strength and the weather resistance of the material are improved, and the reliable production and application of the PCB are facilitated.
In the description of the present specification, the descriptions of the terms "one embodiment," "certain embodiments," "an exemplary embodiment," "an example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While the foregoing is directed to the preferred embodiments of the present application, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the application, such changes and modifications are also intended to be within the scope of the application.
Claims (10)
1. The silver plating lamination method for the printed circuit board base material is characterized by comprising the following steps of:
immersing the copper-clad plate into chemical silver plating liquid containing a sulfhydryl silane coupling agent, and cleaning and drying after the reaction to obtain a silver-plated plate with the surface modified with the silane coupling agent;
immersing the silver plate into a second solution containing a methacryloxy silane coupling agent, and drying after the reaction to obtain a modified substrate self-assembled with a methacryloxy molecular chain;
and pressing the modified substrate and the plastic sheet immersed with the resin adhesive.
2. The silver plating press fit method of a printed circuit board substrate according to claim 1, wherein the copper-clad plate is subjected to pretreatment, and the pretreatment step comprises:
degreasing the copper-clad plate by using an alkaline solution, cleaning the copper-clad plate by using deionized water and ethanol in sequence, and drying; and then microetching the copper-clad plate by using an acid solution, cleaning the copper-clad plate by using deionized water and ethanol in sequence, and drying the copper-clad plate.
3. The method of silver plating lamination of a printed circuit board substrate according to claim 2, wherein the step of degreasing the copper-clad plate with an alkaline solution comprises:
and (3) placing the copper-clad plate in an alkaline solution consisting of 50g/L sodium hydroxide and 50g/L sodium carbonate to remove oil for 5min.
4. The silver plating press fit method of a printed circuit board substrate according to claim 2, wherein the step of microetching the copper-clad plate with an acidic solution comprises:
and microetching the copper-clad plate for 1min by using 125g/L sodium persulfate solution.
5. The method of silver plating press fit for a printed circuit board substrate according to claim 1, wherein the electroless silver plating solution further comprises a complexing agent, a reducing agent and 1wt% to 10wt% silver nitrate.
6. The method for silver plating and laminating a printed circuit board substrate according to claim 5, wherein the step of preparing the electroless silver plating solution comprises:
mixing absolute ethyl alcohol and deionized water to obtain a first solvent, and dissolving a mercaptosilane coupling agent in the first solvent according to the concentration of 1-15wt% to obtain a first solution, wherein the ratio of the mercaptosilane coupling agent to the deionized water is 1:1-5;
adding the silver nitrate while stirring the first solution;
and adding the complexing agent and the reducing agent to obtain the chemical silver plating solution.
7. The method for silver plating and laminating a printed circuit board substrate according to claim 6, wherein the step of immersing the copper-clad plate in the chemical silver plating solution containing the mercapto silane coupling agent, and cleaning and drying after the reaction comprises the steps of:
immersing the copper-clad plate into chemical silver plating solution containing sulfhydryl silane coupling agent, reacting for 0.5-3 h at 20-60 ℃, washing with absolute ethyl alcohol, and drying.
8. The method of silver plating press fit of a printed circuit board substrate according to claim 5, wherein the preparing step of the second solution comprises:
mixing absolute ethyl alcohol and deionized water to obtain a second solvent, dissolving a methacryloxy silane coupling agent in the second solvent according to the concentration of 1-15 wt%, and regulating the pH to 3-5 by acetic acid to obtain a second solution, wherein the ratio of the methacryloxy silane coupling agent to the deionized water is 1:1-5.
9. The silver plating press-fit method of a printed circuit board substrate according to claim 8, wherein the step of immersing the silver-plated plate in a second solution containing a methacryloxy silane coupling agent, and drying after the reaction comprises:
immersing the silver plate into a second solution containing a methacryloxy silane coupling agent, reacting for 5min-60min at 20-60 ℃, and then baking for 0.5h-3h in an environment of 50-100 ℃.
10. The silver plating press-fit method of a printed circuit board substrate according to claim 1, wherein the step of press-fitting the modified substrate with a plastic sheet impregnated with a resin adhesive comprises:
and pressing the modified substrate with a polypropylene plastic sheet immersed with a resin adhesive or a polyimide plastic sheet immersed with the resin adhesive, wherein the pressure is 2MPa-20MPa, the temperature is 150-240 ℃, and the pressing time is 0.5-5 h.
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